Azinediones



United States Patent() 3,408,348. AZINEDIONES James C. Martin and Ronald H. Meen, Kingsport, Tenn .assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey g No Drawing. Filed May 26, 1966, Ser. No; 553,029 7 Claims. (Cl. 260-243) ABSTRACT OF THE DISCLOSUREJ The preparation of oxazinediones and thiazinediones by reacting a malonyl chloride with an aryl or heterocyclic amide or thioamide. The oxazinediones and thiazinediones can be reacted with alcohol to form N-acylm-alonamates and N-thioacylmalonamates which are useful as plasticizers for resins such as cellulose acetate.

scribed in the literature. In a rcentarticle by Ziegler and Meindl in Monatsh. Chem., 95, 1318 (1964) the reaction of monosubstituted malonyl chlorides with aromatic amides to obtain the enol form of certain 4H-1,3-oxazine- 4,6(5H)-diones is revealed. The authors state that disubstituted malonyl chlorides do not react with aromatic amides.

It is an object of this invention to provide certain thiazinediones as novel compositions of matter;

Another object is to provide a method for combining substituted malonyl chlorides with aromatic or heterocyclic amides and with aromatic or heterocyclic thioamides.

Still another object is to present a method for the preparation of certain oxazinediones and thiazinediones.

These and other objects are attained by the practice of this invention which, briefly, comprises mixing a disubstituted malonyl chloride with aromatic or heterocyclic amides or thioamides in an inert solvent either with or without a hydrogen ing the product.

Morespecifically-the processof thisinvention comprises reacting an amide or thioamide having the formula chloride acceptor and isolat- Patented Oct. 29, 196 8 "ice consisting of aryl having from 6 to 14 carbon atoms'and heterocyclic groups containing from 4 to 7 carbon atoms inthe heterocyclic nucleus; each of the substituents R and R when taken singly, are alkyl having from 1 to 8 carbon atoms and mononuclear aryl having from 6 tov 10 carbon atoms; and the substituents R and R when taken collectively with the carbon atom to which they are attached, represent joined alkylene groups completing a carbocyclic ring of 4 to 6 ring carbon atoms. g

The amides that are useful in this invention are well known compounds and may be prepared by a variety of methods. Suitable amides include the following compounds:

ben zamide, I p-chlorobenzamide, o-ethoxybenzamide, m-nitrobenzamide, Z-pyridinecarboxamide, 2-naphthalenecarboxamide, Z-furamide,

p-toluamide, etc.

The thioamides that are used in this invention are well-known compounds and may be prepared by a variety of methods. A few examples of the thioamides that are suitable are:

thiobenzamide, p-chlorothiobenzamide, m-nitrothiobenzamide, 2-thiofuramide, etc.

The substituted malonyl chlorides that are suitable for the present process include the following:

diphenylmalonyl chloride, dimethylmalonyl chloride, diethylmalonyl chloride, ethylmethylmalonyl chloride, dibutylmalonyl chloride, butylethylmalonyl chloride, meth-ylpropylm-alonyl chloride, dioctylmalonyl chloride, butyloctylmalonyl chloride, pentamethylenemalonyl chloride, dibenzylmalonyl chloride, etc.

These compounds may be prepared according to known techniques by reacting the corresponding dialkylmalonic acid with thionyl chloride or a similar chlorinating agent.

In the practice of this invention, for best operation, a hydrogen chloride acceptor material is not used. It is preferred to let the hydrogen chloride, that is evolved dur- '-ing the course of the reaction, volatilize.

, In the process for preparing the 4H-1,3-oxazine-4,6

(5H)-diones and 4H-1,3-thiazine-4,6(5H)-diones, by reacting the substituted malonyl chlorides with the amides or thioamides, it is preferred, but not necessary, to use a solvent. Suitable solvents include those that are substantially unatfected by dry hydrogen chloride. Classes of such solvent materials are aliphatic and aromatic hydrocarbons and chlorinated hydrocarbons and aliphatic and aromatic nitro compounds.

The temperature of the subject reaction is generally governed by the nature of the reactants with the suitable reaction temperature within the range of from 25 to 250 C. However, most of the reagents combine readily at temperatures ranging from 60 to C.

The compounds produced by the present invention are useful as intermediates in the preparation of plasticizers for various resins. A 4H-1,3-thiazine-4,6(5H)-dione or a 4H-l,3-oxazine-4,6(5H)-dione of the present invention may be reacted with an alcohol to produce the respective esters, N-thioacylmalonamates and N-acylmalonamates.

The resulting N-acylmalonamates and -ll-thioacylrnalonamates are useful as plasticizers for various resins such as cellulose acetate butyrate. The resin and a N-acylmalonamate or N-thioacylmalonamate may be milled together on heated rolls to form a plastic having good quality and appearance.

Suitable alcohols which may be used in the reaction for forming N-acylmalonamates and N-thioacylrnalonamates include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, -butyl alcohol, isobutyl alcohol, octyl alcohol, isooctyl alcohol, decyl alcohol, lauryl alcohol, benzyl alcohol, etc. Phenols and substituted phenols are also suitable.

EXAMPLE 1 EXAMPLE 2 A mixture of o-toluamide (21.2 g.; 0.157 mole), dimethylmalonyl chloride (27.0 g.; 0.16 mole) and ethylene dichloride (150 ml.) was refluxed for 10 hrs. The solvent was removed under vacuum to give 38.9 g. of solid residue. Recrystallization from carbon tetrachloride afforded 28.9 g. of 5,5-dimethyl-2-o-tolyl-4H-1,3 oxazine-4,6(H)- dione, M.P. 124-125 C. The following equation represents the reaction that occurred.

A nalysis.--Calcd. C H NO C, 67.5; H, 5.7; N, 6.0. Found: C, 67.3; H, 5.9; N, 6.1.

EXAMPLE 3 i A solution of thiobenzamide (27.4 g.; 0.2 mole) and dimethylmalonyl chloride (37.2 -g.; 0.22 mole) in ethylene dichloride ml.) was refluxed for 3 hrs. Removal of the solvent under vacuum afforded 52 g. of crude product. Recrystallization of this material from carbon tetrachloride to give 41 g. of 5,5dimethyl-2-phenyl-4H-1,3-thiazine-4,6(5H)-dione, M.P. 5658 C. The reaction that occurred is represented by the following equation.

s Q-t'inm (omnowool Analysis.--Calcd. for C H NO S: C, 61.8; H, 4.8; N, 6.0. Found: C, 61.8; H, 4.4; N, 5.6.

EXAMPLE 4 A mixture of Zfuramide (30 g.; 0.27 mole), dimethylmalonyl chloride (50.6 g.; 0.3 mole) and ethylene dichloride (250 ml.) was refluxed for 8 hrs. Evaporation of the solvent gave a solid residue that after recrystallization from a mixture of hexane and benzene gave 51.4 g. of 2 (Z-furyl)-5,5-dimethyl-4H-1,3-oxazine-4,6(5H)- dione. The reaction that took place is illustrated by the following equation I Under the general conditions and process of Example 1, the following substituted malonyl chlorides and amides react to give the products shown.

Amide Malonyl Chloride J1; Product ON 2 (I? O 01H! 0-0 C3H7 im, moon, @n 0 *crr, N-c om omjrotoool), 0 v ll RKL/NH: with a malonyl chloride having the formula at a temperature of about C. to about 250 C. and in the presence of an inert solvent to obtain a compound having the formula wherein X is selected from the group consisting of oxygen and sulfur; the substituent IR is aryl selected from phenyl, tolyl, ethoxyphenyl, nitrophenyl, naphthyl, or chlorophenyl or a heterocyclic group selected from furyl, pyridyl, or thienyl; each of the substituents R and R when taken singly, is phenyl or alkyl having from 1 to 8 carbon atoms; and the substituents R and R when taken collectively with the carbon atom to which they are attached, represent joined alkylene groups completing a carbocyclic ring of 4 to 6 ring carbon atoms.

2. A process according to claim 1 wherein the reaction is carried out in the presence of a hydrogen chloride acceptor material.

3. A thiazinedione having the formula wherein the substituent R is aryl selected from phenyl, tolyl, ethoxyphenyl, nitrophenyl, naphthyl, or chlorophenyl or a heterocyclic group selected from furyl, pyridyl, or thienyl; each of the substituents R and R when taken singly, is phenyl or alkyl having from 1 to 8 carbon atoms; and the substituents R and R whentaken collectively with the carbon atom to which they areattached, represent joined alkylene groups completing a carbocyclic ring of 4 to 6 ring carbon atoms.

4. A compound as defined in claim 3 having the formula 5. A compound as defined .in.c1aim.,.3 ,hauing,he .JEA,compound,as defingdin claim '3 he gqg lhe formula I formula N-fif 0 O 10 References Cited I UNITED STATES PATEEISQ 3,004,971 10/1961 Skinner er a1 "mo -243' 3,336,305 8/1967 Scarborough et a1. 2 6 O-.2,43

6. A compound as defined in claim 3 having the 5 OTHER REFERENCES formula Ziegler et al.: Monat l;. ,Chem., vol. 95, pp. 1318-28 Goerdeler et aL: Chemische Berichte,"vol:" 93, pp'. 6718 ,(1960) QD 1. D42. 20

(H) CH3 HENRY R. JILES, Primary Examiner.

N-G/ \CH3 NORMA s. MILESTONE, Examiner.

('5 J. M. FORD, Asgistani Eqcqminer. i 

